# Patent

## Title
Processes for hydrofluorination of 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane

## Abstract

A process for making 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of contacting 2-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of a catalyst having about 25 to about 99.9 mole percent antimony pentachloride and about 0.1 to about 75 mole percent of a metal of a Lewis acid under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane. There is a second process for making 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of hydrofluorinating about 75 to about 99.9 mole percent 2-chloro-3,3,3-trifluoropropene and about 0.1 to about 25 mole percent of one or more other hydrocarbons having at least one chlorine atom in the presence of a catalyst of fluorinated antimony pentachloride under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane. There is yet another process for hydrofluorinating 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of contacting the 2-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of a vapor phase catalyst under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane.

## Background
CROSS-REFERENCE TO A RELATED APPLICATION
The present application claims priority based upon U.S. Provisional Application Ser. No. 61/073,186, filed Jun. 17, 2008, which is incorporated herein by reference in its entirety.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to processes for the hydrofluorination of 2-chloro-3,3,3-trifluoropropene(1233xf) to 2-chloro-1,1,1,2-tetrafluoropropane(244bb).
2. Description of the Related Art
Antimony halides have previously been described as useful as catalysts in the hydrofluorination of 1233xf to 244bb. Antimony pentachloride has been observed to be particularly active in catalyzing the hydrofluorination reaction (as disclosed in U.S. Provisional Patent Application 61/021,121, filed Jan. 22, 2008) but sometimes induces overfluorination of 1233xf to form pentafluoro compounds, such as 1,1,1,2,3-pentafluoropropane(245cb). 245cb has a lower boiling point than the desired 244bb product, which makes it difficult and costly to separate and remove. Antimony pentachloride can still be employed as a catalyst, but a lengthy induction or conditioning period is necessary to allow the catalyst to age.
It would be desirable to have a process for hydrofluorination of 1233xf to 244bb in which the induction period would be substantially reduced or eliminated. It would also be desirable to have a process for hydrofluorination of 1233xf to 244bb with improved yield and selectivity.
SUMMARY OF THE INVENTION
According to the present invention, there is a process for hydrofluorinating 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of contacting the 2-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of a catalyst having about 25 to about 99.9 mole percent antimony pentachloride and about 0.1 to about 75 mole percent of a metal of a Lewis acid under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane. The metal of a Lewis acid is preferably selected from among SbCl3, TiCl4, SnCl4, TaCl5, NbCl5, NbCl3, ZrCl4, and HfCl4.
Further according to the present invention, there is a process for making 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of hydrofluorinating about 75 to about 99.9 mole percent 2-chloro-3,3,3-trifluoropropene and about 0.1 to about 25 mole percent of one or more other hydrocarbons having at least one chlorine atom in the presence of a catalyst of fluorinated antimony pentachloride under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane.
Still further according to the present invention, there is process for hydrofluorinating 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane, comprising contacting the 2-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of a vapor phase catalyst under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane.


DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the problem of an overactive fluorinated antimony pentachloride (SbCl5) catalyst is addressed by two techniques. The first technique is to intermix with the SbCl5 a minor proportion of a fluorinated Lewis acid catalyst to moderate the reaction rate. The second technique is to admix a minor proportion of one or more other hydrocarbons having at least one chlorine atom with the 1233xf starting material. The hydrocarbons are underfluorinated relative to 1233xf and reduce the effective activity of the catalyst. Essentially, in the first technique, the composition of the catalyst is modified, and, in the second technique, the composition of the starting reactant is modified. The two techniques can be employed separately or in combination.
In the first technique, the fluorinated Lewis acid catalyst is intermixed with antimony pentachloride prior to fluorination such that the catalyst composition has about 25 mole percent to about 99.9 mole percent antimony pentachloride and about 0.1 mole percent to about 75 mole percent fluorinated Lewis acid catalyst. Preferably, the catalyst composition is about 50 mole percent to about 98 mole percent antimony pentachloride and about 2 mole percent to about 50 mole percent fluorinated Lewis acid catalyst. The fluorinated Lewis acid is preferably selected from among SbCl3, TiCl4, SnCl4, TaCl5, NbCl5, NbCl3, ZrCl4, and HfCl4. Most preferably, the catalyst composition is about 75 mole percent to about 95 mole percent antimony pentachloride and about 5 mole percent to about 25 mole percent fluorinated Lewis acid catalyst. The fluorinated Lewis acid is preferably selected from among SbCl3, TiCl4, SnCl4, TaCl5, NbCl5, NbCl3, ZrCl4, and HfCl4. Mixing of the antimony pentachloride and the fluorinated Lewis acid catalyst can be accomplished by any means known in the art.
In the second technique, the 1233xf reactant is admixed with a minor proportion of one or more other hydrocarbons containing at least one chlorine atom such that 1233xf is present from about 75 to about 99.9 mole percent and the one or more hydrocarbons are present from about 0.1 to about 25 mole percent. Preferably, the 1233xf is present from about 85 to about 99.5 mole percent and the one or more hydrocarbons are present from about 0.5 to about 15 mole percent. Most preferably, the 1233xf is present from about 90 to about 99 mole percent and the one or more hydrocarbons are present from about 1 to about 10 mole percent.
Useful other hydrocarbons include those containing at least one chlorine atom. Examples of hydrocarbons having at least one chlorine atom; 1,1,2,3-tetrachloropropene; 2,3-dichloro-3,3-difluoropropene; 2,3,3-trichloro-3-fluoropropene; and 1,1,1,2,3-pentachloropropane (HCC-240db). Also useful are those generating 2-chloro-3,3,3-trifluoropropene or 2-chloro-1,1,1,2-tetrafluoropropane. These compounds are particularly useful as they will all result in the desired 2-chloro-1,1,1,2-tetrafluoropropane or an intermediate that will convert to 2-chloro-1,1,1,2-tetrafluropropane.
For either technique, the hydrofluorination reaction is carried out under conditions sufficient to form 244bb (2-chloro-1,1,1,2-tetrafluoropropane). The reaction is preferably carried out at a temperature of about 30° C. to about 200° C., more preferably about 50° C. to about 150° C., and most preferably about 75° C. to about 125° C. The reaction is preferably carried out at a pressure of about 5 psia (pounds per square inch absolute) to about 200 psia, more preferably about 30 psia to about 175 psia, and most preferably about 60 psia to about 150 psia. The reaction is preferably carried out for a residence time of about 1 second to about 300 seconds, more preferably about 30 seconds to about 240 seconds, and most preferably about 40 seconds to about 120 seconds for a continuous process. The reaction can also be carried out in batch process. In case of using batch process, the reaction is preferably carried out for a residence time of about 15 second to about 3600 seconds, more preferably about 60 seconds to about 1800 seconds, and most preferably about 120 seconds to about 300 seconds. Residence time is the reactor volume that contains the liquid phase reactant mixture divided by the volumetric flow rate of the products.
For either technique, the by-product selectivity, i.e., selectivity for products other than the desired 244bb (2-chloro-1,1,1,2-tetrafluoropropane), is less than 15 mole percent, preferably less than 5 mole percent, and most preferably less than 1.5 mole percent.
When reaction is conducted in a vapor phase process, the catalyst may be supported or in bulk form (unsupported). Useful catalyst supports include carbon, alumina, fluorinated alumina, aluminum fluoride, alkaline earth metal oxides, fluorinated alkaline earth metals, zinc oxide, zinc fluoride, tin oxide, and tin fluoride.
The catalyst optionally may be activated prior to and during use. Useful activating agents include anhydrous hydrogen fluoride and chlorine. The catalyst is kept activated by the continuous or batch addition of an oxidizing agent such as Cl2.
The hydrofluorination reaction may be carried out in the liquid phase or the vapor phase. Liquid-phase reactions are preferred.
The following are examples of the present invention and are not to be construed as limiting.
EXAMPLES
In the following examples, 2-chloro-3,3,3-trifluoropropene(1233xf) was fluorinated to 244bb. In Comparative Example 1, using a catalyst system of 100% antimony pentafluoride (SbCl5). In Examples 1 and 2, a catalyst system of antimony pentachloride/antimony trichloride in a 5:1 mole ratio was substituted for the antimony pentafluoride catalyst system of Comparative Example 1. In Example 3, a 2% mix of 1,1,2,3-tetrachloropropene in 98% 2-chloro-3,3,3-trifluoropropene by weight is used early in the run to reduce the activity of the catalyst system, and thereby the formation of 1,1,1,2,2-pentafluoropropane. Example 4 demonstrates the use of vapor phase fluorination of 2-chloro-3,3,3-trifluoropropene to produce 244bb.
In Examples 1 and 2, the mixing of the antimony pentachloride/antimony trichloride was accomplished by adding a weighed amount of antimony pentachloride (liquid) first to a round-bottom flask equipped with a heating mantle, stirring bar, and condenser. A weighed amount of antimony trichloride (solid) was then added to the same flask. The flask was then heated to accomplish dissolution of the trichloride into the mixture and to exceed the melting point of the mixture (40-50 degrees Celsius). The molten catalyst mixture was then transferred to a heated (to prevent selective precipitation) cylinder. Nitrogen was added under pressure to the heated cylinder. The cylinder was connected to the reactor using a flexible tube. The contents of the cylinder was transferred to the reactor by opening a cylinder valve. The cylinder was weighed and compared to the cylinder's empty weight to ascertain that the desired weight transfer had been achieved. Hydrogen fluoride is added to the catalyst to achieve a fluorinated catalyst, which analysis will reveal is a mix of fluoride and chloride.
Comparative Example 1
Comparative Example 1 (Run #38) was a liquid phase fluorination of 2-chloro-3,3,3-trifluoropropene(1233xf) to 244bb using a catalyst system of antimony pentafluoride (SbCl5). Comparative Example 1 demonstrated the effect of a long induction period when the run produced the 1,1,1,2,3-pentafluoropropane(245cb) byproduct in quantities of up to mole 50% by mole early in the Run, decreasing to reasonable levels (below  ̃1.5%) by mole after about 60 hours. Production of 245cb byproduct decreased with the age of the catalyst.
About 4175 grams of new SbCl5 were added into Reactor R11. R11is a TeflonTM-lined liquid phase reactor (Teflon is a trademark of E.I. duPont de Nemours & Co) equipped with a 2-inch ID (inside diameter) catalyst stripper (a packed column to keep catalyst from escaping from the reactor system). The reactor is 2.75-inch ID×36-inch L (length). The reactor was heated to about 85° C.-87° C. HF feed was started first. After 1.3 lbs (pounds) of HF had been added to fluorinate the catalyst charge, the 2-chloro-3,3,3-trifluoropropene feed was started. The purity of the 2-chloro-3,3,3-trifluoropropene feed stock was about 98 GC Area % (gas chromatograph). The experiment ran continuously for about 136 hours. For this run, Cl2 was fed batchwise about every 4 hours throughout the run in case needed to keep the catalyst active. The HF and 2-chloro-3,3,3-trifluoropropene feeds were varied during the run. The feeds averaged 0.495 lbs/hr (pounds/hour) HF, and 0.408 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 5.4% by weight of organic) for a 7.9/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 135 seconds residence time. In the middle of the run, the feeds averaged 0.843 lbs/hr HF and 0.66 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 3.3% by weight of organic) for a 8.33/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 80 seconds residence time. For the end of the run, the rate was increased. The feeds for this period averaged 1.42 lbs/hr HF and 1.24 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 2% by weight of organic) for a 7.5/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 47 seconds residence time. The reactor temperature range for the experiment was 78-91° C. and the pressure range was 85 psig-115 psig (pounds per square inch gauge). Results on a molar basis are set forth in Table 1 below.







TABLE 1







(Run #38, Conversion and Selectivity on a Molar Basis)
















hours

HF/Org
Residence
molar
molar
molar
molar
molar
molar


el.
Temp
mole
Time,
selectivity
selectivity
Conversion
selectivity
selectivity
selectivity


Time
° C.
ratio
seconds
245cb
244bb
1233xf
235da
1232xf
1223xd



















2.5
82.9
5.28
69.24
0.402
0.528
0.977
0.013
0.011
0.041


3.5
85.6
7.17
74.50
0.452
0.466
0.961
0.001
0.009
0.053


4.5
88
7.56
80.85
0.558
0.347
0.952
0.002
0.008
0.068


5.5
88.4
10.38
64.93
0.561
0.332
0.939
0.005
0.008
0.072


6.5
87.7
8.72
56.54
0.583
0.344
0.966
0.006
0.004
0.040


7.5
85.9
5.40
52.12
0.563
0.395
0.989
0.009
0.006
0.018


8.5
85.5
5.87
52.77
0.469
0.494
0.985
0.006
0.006
0.015


9.5
83.5
5.91
52.61
0.434
0.521
0.985
0.008
0.006
0.024


10.5
82
6.58
56.63
0.364
0.599
0.981
0.004
0.006
0.014


11.5
80.9
7.50
52.38
0.364
0.603
0.981
0.004
0.007
0.015


12.5
80.6
6.00
44.62
0.309
0.671
0.981
0.002
0.005
0.009


13.5
87.3
4.38
61.76
0.459
0.520
0.984
0.003
0.002
0.009


14.5
85
11.92
102.18
0.529
0.452
0.985
0.004
0.002
0.008


15.5
84.3
5.99
75.06
0.463
0.525
0.986
0.002
0.003
0.005


16.5
81.4
4.78
77.95
0.303
0.690
0.985
0.001
0.004
0.001


17.5
83.9
6.42
55.81
0.265
0.725
0.981
0.001
0.003
0.004


18.5
80.4
4.45
50.35
0.287
0.707
0.983
0.000
0.004
0.001


19.5
84
5.19
52.11
0.207
0.785
0.977
0.001
0.003
0.002


20.5
86.8
9.09
64.88
0.338
0.624
0.982
0.008
0.005
0.017


22.5
86
5.28
46.71
0.500
0.482
0.985
0.003
0.004
0.008


23.5
91.1
7.48
65.28
0.572
0.300
0.988
0.001
0.004
0.002


24.5
89.3
6.11
65.07
0.381
0.607
0.986
0.001
0.005
0.002


25.5
88
5.72
61.20
0.302
0.677
0.985
0.002
0.004
0.009


26.5
86.2
5.49
65.89
0.240
0.753
0.983
0.001
0.002
0.002


28.5
83.2
5.36
61.61
0.074
0.898
0.980
0.000
0.002
0.002


30.5
88.4
7.03
58.43
0.137
0.854
0.977
0.000
0.002
0.002


31.5
81.5
12.65
79.12
0.175
0.814
0.974
0.000
0.003
0.002


32.5
77.4
8.29
53.93
0.152
0.839
0.981
0.000
0.002
0.001


33.5
77.8
6.58
64.39
0.141
0.848
0.984
0.000
0.003
0.001


34.5
81.9
7.42
57.13
0.077
0.917
0.980
0.000
0.002
0.002


35.5
82
6.94
62.47
0.0605
0.9276
97.9
0.0008
0.0025
0.0069


36.5
81.7
7.47
56.94
0.1020
0.8732
97.6
0.0013
0.0036
0.0168


37.5
82.6
7.05
61.49
0.0437
0.9281
97.7
0.0011
0.0021
0.0158


38.5
84.1
6.63
56.90
0.0480
0.9382
97.7
0.0003
0.0016
0.0022


39.5
84.7
7.53
63.86
0.0507
0.9322
97.7
0.0002
0.0016
0.0018


40.5
85.8
6.42
59.09
0.0686
0.9205
97.0
0.0003
0.0017
0.0016


41.5
85.8
6.64
60.83
0.0874
0.8955
97.2
0.0011
0.0029
0.0056


42.5
86.7
6.90
66.22
0.0598
0.9292
97.6
0.0003
0.0020
0.0031


43.5
85.3
6.06
64.12
0.0480
0.9433
97.3
0.0002
0.0017
0.0015


45.5
81.6
3.75
54.60
0.0176
0.9756
97.8
0.0002
0.0020
0.0023


47.5
82.6
4.35
62.86
0.0212
0.9664
97.7
0.0002
0.0018
0.0017


47.5
82.9
6.61
87.62
0.0184
0.9719
97.7
0.0002
0.0014
0.0013


48.5
83.4
15.10
132.60
0.0235
0.9655
97.8
0.0003
0.0014
0.0012


50.5
81.8
3.52
48.35
0.0136
0.9756
97.8
0.0000
0.0016
0.0015


51.5
82
4.66
51.54
0.0155
0.9729
97.5
0.0001
0.0018
0.0012


52.5
84.8
4.96
53.28
0.0203
0.9620
96.7
0.0011
0.0026
0.0063


53.5
86
4.67
61.03
0.0224
0.9648
96.5
0.0003
0.0022
0.0027


54.5
91.7
5.28
69.24
0.0171
0.9722
97.2
0.0003
0.0018
0.0013


55.5
86.8
4.37
78.61
0.0233
0.9564
97.6
0.0017
0.0024
0.0070


56.5
85.6
4.56
77.59
0.0208
0.9571
97.5
0.0010
0.0017
0.0124


57.5
84.5
4.91
62.45
0.0168
0.9734
97.4
0.0005
0.0017
0.0030


58.5
85.8
4.31
81.33
0.0181
0.9715
97.3
0.0004
0.0013
0.0021


35.5
82
6.94
62.47
0.0605
0.9276
97.9
0.0008
0.0025
0.0069


36.5
81.7
7.47
56.94
0.1020
0.8732
97.6
0.0013
0.0036
0.0168


37.5
82.6
7.05
61.49
0.0437
0.9281
97.7
0.0011
0.0021
0.0158


38.5
84.1
6.63
56.90
0.0480
0.9382
97.7
0.0003
0.0016
0.0022


39.5
84.7
7.53
63.86
0.0507
0.9322
97.7
0.0002
0.0016
0.0018


40.5
85.8
6.42
59.09
0.0686
0.9205
97.0
0.0003
0.0017
0.0016


41.5
85.8
6.64
60.83
0.0874
0.8955
97.2
0.0011
0.0029
0.0056


42.5
86.7
6.90
66.22
0.0598
0.9292
97.6
0.0003
0.0020
0.0031


43.5
85.3
6.06
64.12
0.0480
0.9433
97.3
0.0002
0.0017
0.0015


45.5
81.6
3.75
54.60
0.0176
0.9756
97.8
0.0002
0.0020
0.0023


47.5
82.6
4.35
62.86
0.0212
0.9664
97.7
0.0002
0.0018
0.0017


47.5
82.9
6.61
87.62
0.0184
0.9719
97.7
0.0002
0.0014
0.0013


48.5
83.4
15.10
132.60
0.0235
0.9655
97.8
0.0003
0.0014
0.0012


50.5
81.8
3.52
48.35
0.0136
0.9756
97.8
0.0000
0.0016
0.0015


51.5
82
4.66
51.54
0.0155
0.9729
97.5
0.0001
0.0018
0.0012


52.5
84.8
4.96
53.28
0.0203
0.9620
96.7
0.0011
0.0026
0.0063


53.5
86
4.67
61.03
0.0224
0.9648
96.5
0.0003
0.0022
0.0027


54.5
91.7
5.28
69.24
0.0171
0.9722
97.2
0.0003
0.0018
0.0013


55.5
86.8
4.37
78.61
0.0233
0.9564
97.6
0.0017
0.0024
0.0070


56.5
85.6
4.56
77.59
0.0208
0.9571
97.5
0.0010
0.0017
0.0124


57.5
84.5
4.91
62.45
0.0168
0.9734
97.4
0.0005
0.0017
0.0030


58.5
85.8
4.31
81.33
0.0181
0.9715
97.3
0.0004
0.0013
0.0021


59.5
85.1
7.04
77.61
0.0207
0.9673
97.6
0.0010
0.0018
0.0023


60.5
84.1
9.44
92.17
0.0143
0.9688
97.5
0.0009
0.0011
0.0060


61.5
83.3
5.68
79.80
0.0115
0.9769
97.5
0.0007
0.0014
0.0043


62.5
83.2
4.42
68.37
0.0116
0.9759
97.6
0.0000
0.0014
0.0034


63.5
83.2
4.52
63.10
0.0108
0.9604
97.7
0.0018
0.0017
0.0148


64.5
82.7
9.18
94.88
0.0107
0.9718
97.7
0.0009
0.0013
0.0083


65.5
81.8
9.79
86.54
0.0104
0.9744
97.5
0.0005
0.0011
0.0047


66.5
82.7
8.51
79.63
0.0100
0.9771
97.6
0.0004
0.0010
0.0021


67.5
84.5
7.67
72.39
0.0136
0.9810
97.5
0.0014
0.0009
0.0013


68.5
85
8.31
75.69
0.0127
0.9798
97.4
0.0006
0.0010
0.0027


69.5
84.6
7.28
78.32
0.0131
0.9805
97.4
0.0005
0.0009
0.0018


70.5
87.9
7.41
75.96
0.0119
0.9792
97.4
0.0003
0.0009
0.0019


71.5
84.2
3.23
82.17
0.0136
0.9594
97.5
0.0016
0.0012
0.0204


72.5
85.2
3.97
75.69
0.0132
0.9782
97.5
0.0004
0.0012
0.0026


73.5
85.7
5.23
65.87
0.0145
0.9755
97.3
0.0003
0.0013
0.0020


74.5
85.1
4.59
81.36
0.0143
0.9760
96.9
0.0003
0.0012
0.0018


75.4
82.9
10.88
84.53
0.0121
0.9781
97.0
0.0003
0.0012
0.0020


76
84.7
5.72
83.19
0.0120
0.9761
97.5
0.0011
0.0016
0.0033


77
84.2
4.54
69.59
0.0151
0.9670
97.4
0.0009
0.0013
0.0106


78
83.7
6.37
84.65
0.0145
0.9779
97.3
0.0004
0.0009
0.0026


80
81.8
6.31
80.21
0.0100
0.9855
97.7
0.0002
0.0010
0.0017


81
81.9
8.43
65.81
0.0084
0.9867
97.5
0.0006
0.0009
0.0018


82
80.6
8.36
61.56
0.0079
0.9807
97.6
0.0011
0.0013
0.0071


83
79.3
7.88
74.86
0.0110
0.9644
97.5
0.0029
0.0017
0.0178


84
82.5
7.46
63.51
0.0078
0.9577
97.6
0.0017
0.0014
0.0194


85
82.4
7.70
73.91
0.0079
0.9600
97.7
0.0016
0.0014
0.0181


85.5
82.1
9.70
79.88
0.0076
0.9761
97.7
0.0006
0.0013
0.0046


86
82.2
8.55
72.14
0.0069
0.9755
97.5
0.0005
0.0011
0.0024


87
82.3
7.48
65.28
0.0074
0.9766
97.5
0.0005
0.0011
0.0019


89.5
84.6
10.13
66.51
0.0072
0.9830
97.2
0.0008
0.0011
0.0030


90.5
84.9
10.66
79.39
0.0074
0.9822
97.4
0.0004
0.0009
0.0016


92.5
84.2
7.99
60.49
0.0087
0.9743
97.5
0.0066
0.0009
0.0019


93.5
84.3
4.64
54.84
0.0066
0.9872
97.2
0.0004
0.0010
0.0016


94.5
83.8
5.09
58.42
0.0069
0.9871
97.3
0.0003
0.0010
0.0012


96.5
82.6
4.91
56.99
0.0075
0.9824
97.0
0.0005
0.0011
0.0045


97.5
82.3
5.97
62.30
0.0062
0.9886
97.4
0.0002
0.0011
0.0012


99.5
80.3
5.61
57.78
0.0062
0.9891
97.4
0.0003
0.0010
0.0020


100.5
80.4
5.93
60.90
0.0043
0.9899
97.3
0.0002
0.0015
0.0029


103.7
80.5
5.74
63.18
0.0049
0.9838
97.1
0.0002
0.0013
0.0019


106
82.2
12.23
81.85
0.0055
0.9855
96.8
0.0006
0.0010
0.0042


107
84.3
6.96
56.74
0.0053
0.9889
95.3
0.0000
0.0010
0.0012


108
84.3
4.97
74.03
0.0095
0.9750
92.5
0.0012
0.0015
0.0095


109
86.5
4.67
77.77
0.0120
0.9719
94.1
0.0009
0.0015
0.0109


110
86
5.60
70.37
0.0073
0.9851
96.0
0.0004
0.0011
0.0033


111
85.5
5.50
73.61
0.0066
0.9880
96.6
0.0001
0.0015
0.0015


112
83.4
5.45
69.12
0.0067
0.9687
97.0
0.0031
0.0016
0.0139


113
83.8
6.11
65.68
0.0049
0.9820
97.4
0.0006
0.0011
0.0054


114
83.3
5.86
74.89
0.0053
0.9859
97.4
0.0004
0.0011
0.0029


115
82.5
6.11
76.87
0.0042
0.9846
97.4
0.0003
0.0012
0.0019


116
82.6
3.85
84.01
0.0056
0.9753
97.4
0.0011
0.0009
0.0136


117
83.8
3.05
71.88
0.0053
0.9847
97.4
0.0005
0.0010
0.0056


120.2
83.7
4.74
54.08
0.0158
0.9744
97.3
0.0014
0.0006
0.0040


122.2
84.5
8.96
48.74
0.0136
0.9674
96.8
0.0023
0.0009
0.0117


123.2
83.9
6.82
52.42
0.0129
0.9720
96.6
0.0015
0.0009
0.0087


124.2
83.2
6.67
52.11
0.0136
0.9731
96.0
0.0013
0.0009
0.0068


125.2
83.7
7.27
51.45
0.0128
0.9735
93.8
0.0016
0.0010
0.0062


126.2
82.9
7.34
49.36
0.0113
0.9671
92.2
0.0025
0.0012
0.0127


127.2
82.5
6.15
59.07
0.0133
0.9686
85.3
0.0020
0.0013
0.0094


128.2
84.2
6.30
61.03
0.0152
0.9664
83.4
0.0020
0.0013
0.0083


129
86.6
4.84
88.11
0.0137
0.9471
83.7
0.0056
0.0016
0.0061


129.7
85.8
6.42
58.11
0.0144
0.9629
84.7
0.0032
0.0013
0.0061


131.2
85.6
12.30
74.60
0.0144
0.9645
82.4
0.0039
0.0014
0.0078


132.5
85.2
10.24
72.82
0.0055
0.9791
48.1
0.0000
0.0017
0.0069


134.3
85.9
7.64
75.01
0.0046
0.9849
53.9
0.0010
0.0016
0.0025


135.5
85.2
6.66
72.78
0.0038
0.9521
43.1
0.0000
0.0015
0.0356









Example 1
In Example 1, a catalyst system of SbCl5/SbCl3 in a 5:1 mole ratio was employed. About 1988 grams of new SbCl5 were mixed with about 280 grams of new SbCl3. The mixture was heated to achieve homogeneity. The combined mix was added into Reactor R11. R11 is a TeflonTM-lined liquid phase reactor (Teflon is a trademark of E. I. duPont de Nemours & Co) equipped with a 2-inch ID (inside diameter) catalyst stripper (a packed column to keep catalyst from escaping from the reactor system). The reactor is 2.75-inch ID×36-inch L (length). The reactor was heated to about 85° C.-87° C. HF feed was started first. After 1.3 lbs (pounds) of HF had been added to fluorinate the catalyst charge, the 2-chloro-3,3,3-trifluoropropene feed was started. The purity of the 2-chloro-3,3,3-trifluoropropene feed stock was about 98 GC area % (gas chromatograph). The experiment (Run#47) ran continuously for about 14 hours. For this run, Cl2 was fed batchwise about every 4 hours throughout the run in case needed to keep the catalyst active. The HF and 2-chloro-3,3,3-trifluoropropene feeds were varied during the run. Overall, the feeds averaged 1.09 lbs/hr HF (0.93 lbs/hr in the early portion of the run, 1.18 lbs/hr in the middle portion of the run, and 1.16 lbs/hr in the latter portion of the run), and 0.84 lbs/hr 2-chloro-3,3,3-trifluoropropene (1.07 lbs/hr in the early portion of the run, 0.6 lbs/hr in the middle portion, and 0.86 lbs/hr in the latter portion of the run) (chlorine was 5.4% by weight of organic) for a 12.4/1 ratio of HF/2-chloro-3,3,3-trifluoropropene and 82 seconds residence time. The reactor temperature range for the experiment was 85-100° C. and the pressure range was 85 psig-115 psig (pounds per square inch gauge). The results are set forth in Table 2 below.







TABLE 2







(Run #47 Conversion and Selectivity on a Molar Basis)
















The bold lines indicate periods of shut-down followed by re-start






Example 2
In Example 2, a catalyst system of SbCl5/SbCl3 in a 5:1 mole ratio was employed. About 1937 grams of new SbCl5 were mixed with about 292 grams of new SbCl3. The mixture was heated to achieve homogeneity. The combined mixture was added into Reactor R11. R11 is a TeflonTM-lined liquid phase reactor (Teflon is a trademark of E. I. duPont de Nemours & Co) equipped with a 2-inch ID (inside diameter) catalyst stripper (a packed column to keep catalyst from escaping from the reactor system). The reactor is 2.75-inch ID×36-inch L (length). The reactor was heated to about 85° C.-87° C. HF feed was started first. After 1.3 lbs (pounds) of HF had been added to fluorinate the catalyst charge, the 2-chloro-3,3,3-trifluoropropene feed was started. The purity of the 2-chloro-3,3,3-trifluoropropene feed stock was about 98 GC area % (gas chromatograph). The experiment (Run#48) ran continuously for about 129 hours. For this run, Cl2 was fed batchwise about every 4 hours throughout the run in case needed to keep the catalyst active. The HF and 2-chloro-3,3,3-trifluoropropene feeds were varied slightly during the run. The feeds averaged 0.99 lbs/hr HF, and 0.72 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 5.4% by weight of organic) for a 8.9/1 ratio of HF/2-chloro-3,3,3-trifluoropropene and 89 seconds residence The reactor temperature range for the experiment was 86-103° C. and the pressure range was 85 psig-115 psig (pounds per square inch gauge). Results are shown in Table 3 below.







TABLE 3







(Run #48 Conversion and Selectivity on a Molar Basis)

















hours

HF/Org
Residence
molar
molar
molar
molar
molar
molar
molar


el.
Temp
mole
Time,
selectivity
selectivity
Conversion
selectivity
selectivity
selectivity
selectivity


Time
° C.
ratio
seconds
245cb
244bb
1233xf
235da
1232xf
1223xd
others*




















1
86.3
7.30
114.06
0.0036
0.9749
0.4650
0.0016
0.0037
0.0005
0.0156


1.5
88.1
11.96
147.31
0.0563
0.9011
0.7751
0.0026
0.0073
0.0010
0.0318


2.5
82.4
8.49
86.25
0.1391
0.8004
0.6165
0.0046
0.0025
0.0004
0.0530


3.5
85.5
13.05
114.85
0.1755
0.7593
0.5813
0.0067
0.0052
0.0003
0.0530


4.5
80.6
9.73
100.02
0.2206
0.7255
0.6609
0.0056
0.0065
0.0001
0.0417


5.5
75.6
12.17
89.06
0.3061
0.6602
0.7866
0.0043
0.0057
0.0001
0.0237


7.4
85.7
15.11
63.56
0.0898
0.7812
0.9651
0.0590
0.0356
0.0000
0.0344


8.4
90.3
10.46
77.98
0.3341
0.5772
0.9736
0.0087
0.0471
0.0001
0.0328


9.4
93.1
7.65
81.42
0.1529
0.7600
0.9757
0.0029
0.0315
0.0019
0.0508


10.4
98.4
8.30
78.56
0.1673
0.8147
0.9697
0.0005
0.0056
0.0013
0.0106


11.4
97.7
8.70
94.34
0.1583
0.8295
0.9699
0.0003
0.0033
0.0008
0.0078


12.4
96.1
9.39
90.98
0.1004
0.8896
0.9721
0.0003
0.0027
0.0006
0.0063


13.4
94.9
8.86
76.21
0.1077
0.8836
0.9727
0.0003
0.0025
0.0006
0.0054


14.4
96.3
9.54
74.48
0.0977
0.8955
0.9728
0.0002
0.0018
0.0006
0.0042


15.4
95.7
7.91
98.49
0.0863
0.9074
0.9733
0.0001
0.0016
0.0007
0.0040


16.4
97.1
10.88
84.53
0.0864
0.9066
0.9730
0.0001
0.0016
0.0009
0.0044


17.4
95.8
7.09
84.10
0.0817
0.9120
0.9728
0.0001
0.0016
0.0008
0.0039


18.4
96.4
9.39
90.98
0.0646
0.9297
0.9720
0.0001
0.0015
0.0008
0.0033


19.4
96
9.61
80.24
0.0513
0.9409
0.9721
0.0002
0.0019
0.0013
0.0045


20.4
97
7.87
89.27
0.0529
0.9399
0.9730
0.0002
0.0019
0.0012
0.0039


21.4
96.7
10.62
95.74
0.0490
0.9438
0.9724
0.0004
0.0019
0.0013
0.0036


22.4
98
9.71
67.12
0.0494
0.9399
0.9734
0.0001
0.0028
0.0027
0.0051


23.4
97.4
9.11
105.04
0.0484
0.9448
0.9730
0.0002
0.0015
0.0013
0.0039


24.4
96.9
9.73
100.02
0.0507
0.9443
0.9732
0.0002
0.0014
0.0007
0.0027


25.4
96.5
7.64
75.01
0.0448
0.9495
0.9721
0.0001
0.0016
0.0012
0.0028


26.4
99.6
9.83
80.43
0.0441
0.9493
0.9728
0.0003
0.0015
0.0014
0.0035


27.4
97.3
8.58
85.84
0.0629
0.9326
0.9726
0.0002
0.0010
0.0007
0.0026


28.4
96.7
12.26
90.20
0.0584
0.9353
0.9720
0.0003
0.0014
0.0010
0.0036


29.4
96.5
7.73
81.05
0.0632
0.9318
0.9726
0.0001
0.0010
0.0008
0.0031


30.4
96.7
10.88
84.53
0.0597
0.9363
0.9728
0.0001
0.0008
0.0007
0.0023


31.4
95.6
9.54
91.70
0.0529
0.9434
0.9721
0.0001
0.0008
0.0007
0.0021


32.4
97.1
8.70
94.34
0.0527
0.9438
0.9723
0.0001
0.0008
0.0007
0.0020


33.4
92
9.70
79.88
0.0481
0.9486
0.9717
0.0001
0.0007
0.0006
0.0019


34.4
95.4
10.80
96.53
0.0388
0.9574
0.9706
0.0006
0.0006
0.0007
0.0019


35.4
95.3
8.16
72.87
0.0379
0.9577
0.9708
0.0007
0.0007
0.0009
0.0020


36.4
96.6
8.16
76.00
0.0357
0.9606
0.9687
0.0001
0.0007
0.0007
0.0021


37.4
88.7
9.83
80.43
0.0313
0.9643
0.9704
0.0001
0.0010
0.0010
0.0022


38.4
88
7.04
77.61
0.0365
0.9601
0.9708
0.0001
0.0007
0.0007
0.0019


39.4
87.6
10.88
84.53
0.0419
0.9538
0.9705
0.0005
0.0006
0.0009
0.0022


40.4
87.7
10.18
87.42
0.0392
0.9564
0.9705
0.0006
0.0006
0.0009
0.0022


41.4
87.9
9.12
83.43
0.0356
0.9594
0.9703
0.0006
0.0008
0.0012
0.0022


42.4
88.2
8.38
85.62
0.0335
0.9625
0.9717
0.0001
0.0007
0.0009
0.0022


43.4
88.3
9.73
100.02
0.0268
0.9675
0.9705
0.0006
0.0010
0.0016
0.0025


44.4
88.4
13.28
86.28
0.0236
0.9709
0.9704
0.0006
0.0010
0.0015
0.0024


45.4
89.9
7.67
89.03
0.0229
0.9718
0.9702
0.0006
0.0009
0.0014
0.0024


46.4
89.8
10.18
87.42
0.0227
0.9725
0.9708
0.0004
0.0009
0.0014
0.0021


47.4
89.9
11.39
92.28
0.0209
0.9731
0.9710
0.0004
0.0010
0.0020
0.0026


48.4
89.9
9.62
100.58
0.0214
0.9738
0.9711
0.0006
0.0009
0.0011
0.0021


49.4
91
8.70
94.34
0.0198
0.9758
0.9712
0.0005
0.0008
0.0010
0.0020


50.4
90.9
12.38
89.75
0.0199
0.9762
0.9703
0.0005
0.0008
0.0008
0.0018


51.4
91.1
7.14
91.77
0.0252
0.9718
0.9708
0.0001
0.0006
0.0007
0.0015


52.4
91.2
9.12
83.43
0.0221
0.9743
0.9694
0.0001
0.0007
0.0008
0.0019


53.4
91.8
9.83
80.43
0.0240
0.9728
0.9706
0.0001
0.0006
0.0007
0.0018


54.4
90.9
13.05
114.85
0.0223
0.9744
0.9693
0.0001
0.0007
0.0007
0.0018


55.4
91.1
10.51
96.25
0.0228
0.9736
0.9702
0.0005
0.0006
0.0007
0.0019


56.4
91.4
11.59
93.02
0.0209
0.9755
0.9682
0.0007
0.0006
0.0005
0.0018


57
89.2
NA
NA
0.0041
0.9924
0.9252
0.0005
0.0012
0.0001
0.0017


58
92.2
NA
NA
0.0052
0.9923
0.9508
0.0006
0.0012
0.0002
0.0006


59
94.2
NA
NA
0.0047
0.9727
0.9514
0.0006
0.0201
0.0007
0.0013


60
96.1
NA
NA
0.0051
0.9889
0.9495
0.0004
0.0034
0.0005
0.0018


61
96.1
NA
NA
0.0055
0.9489
0.9356
0.0017
0.0384
0.0013
0.0043


62.6
91.3
NA
NA
0.2850
0.6857
0.9753
0.0027
0.0172
0.0005
0.0088


63.6
87.3
NA
NA
0.0152
0.9787
0.9484
0.0004
0.0016
0.0008
0.0034


64.6
93
NA
NA
0.0128
0.9807
0.9378
0.0007
0.0016
0.0008
0.0034


65.6
91.5
NA
NA
0.0123
0.9791
0.8523
0.0021
0.0028
0.0004
0.0033


66.7
92
NA
NA
0.0098
0.9790
0.9198
0.0014
0.0029
0.0024
0.0046


67.7
96.4
NA
NA
0.0103
0.9749
0.8596
0.0044
0.0023
0.0021
0.0061


68.7
96.5
NA
NA
0.0099
0.9676
0.9066
0.0018
0.0147
0.0009
0.0052


69.7
95.3
NA
NA
0.0099
0.9784
0.9177
0.0010
0.0046
0.0010
0.0051


70.7
94.9
NA
NA
0.0102
0.9722
0.8600
0.0044
0.0023
0.0021
0.0088


71.7
95.0
NA
NA
0.0092
0.9806
0.9299
0.0004
0.0020
0.0026
0.0052


73.1
75.2
NA
NA
0.0075
0.9849
0.8190
0.0014
0.0009
0.0012
0.0041


74.1
93.9
NA
NA
0.0060
0.9843
0.8893
0.0006
0.0034
0.0004
0.0054


76.2
85.4
8.83
46.49
0.0642
0.8920
0.9202
0.0021
0.0246
0.0027
0.0143


77.2
82.6
13.22
63.51
0.3227
0.6648
0.9633
0.0006
0.0040
0.0016
0.0063


78.2
100
9.74
88.05
0.0700
0.9224
0.9774
0.0008
0.0024
0.0001
0.0043


79.2
99.9
6.53
88.05
0.1914
0.8007
0.9786
0.0004
0.0030
0.0004
0.0040


80.2
102.1
10.63
91.05
0.0786
0.9122
0.9760
0.0007
0.0046
0.0001
0.0039


81.2
101.6
9.01
86.28
0.0636
0.9260
0.9747
0.0006
0.0055
0.0003
0.0040


82.2
100.4
7.85
88.15
0.0548
0.9365
0.9740
0.0005
0.0041
0.0006
0.0036


83.2
100.6
10.97
84.13
0.0477
0.9434
0.9726
0.0005
0.0030
0.0014
0.0040


84.2
100.6
8.29
86.03
0.0398
0.9481
0.9747
0.0005
0.0020
0.0034
0.0064


85.2
100.7
8.70
94.34
0.0377
0.9519
0.9754
0.0005
0.0016
0.0028
0.0055


86.2
102.1
11.48
65.33
0.0367
0.9515
0.9751
0.0005
0.0017
0.0024
0.0073


87.4
102.5
11.89
55.41
0.0391
0.9532
0.9715
0.0001
0.0014
0.0021
0.0041


88.4
101.1
9.51
73.70
0.0411
0.9513
0.9701
0.0001
0.0015
0.0018
0.0043


89.4
100.8
7.01
72.05
0.0364
0.9572
0.9734
0.0004
0.0014
0.0010
0.0037


90.4
101.2
11.54
83.17
0.0351
0.9577
0.9737
0.0004
0.0015
0.0014
0.0039


91.4
100.6
9.83
80.43
0.0228
0.9662
0.9754
0.0004
0.0022
0.0030
0.0054


92.4
100.2
7.95
67.55
0.0193
0.9702
0.9758
0.0004
0.0021
0.0028
0.0053


93.4
100.6
11.04
85.15
0.0229
0.9676
0.9758
0.0003
0.0020
0.0026
0.0046


94.4
100.3
10.18
87.42
0.0225
0.9696
0.9759
0.0004
0.0016
0.0019
0.0041


95.4
100.3
9.67
71.32
0.0196
0.9694
0.9759
0.0004
0.0020
0.0031
0.0055


96.4
100.1
9.56
83.86
0.0220
0.9696
0.9753
0.0004
0.0016
0.0019
0.0046


97.4
99.8
10.27
76.61
0.0204
0.9720
0.9763
0.0001
0.0017
0.0021
0.0036


98.4
100.2
13.05
85.65
0.0190
0.9718
0.9760
0.0004
0.0019
0.0023
0.0046


99.4
100.3
12.16
72.01
0.0249
0.9696
0.9746
0.0001
0.0014
0.0013
0.0027


100.4
100.5
11.40
76.66
0.0286
0.9659
0.9754
0.0001
0.0004
0.0013
0.0037


101.4
100.8
15.75
98.37
0.0251
0.9689
0.9756
0.0001
0.0014
0.0014
0.0031


102.4
100.9
10.60
78.50
0.0245
0.9702
0.9752
0.0001
0.0013
0.0011
0.0028


103.4
101.1
10.48
93.20
0.0261
0.9688
0.9755
0.0001
0.0013
0.0011
0.0027


104.4
100.8
12.80
98.25
0.0235
0.9708
0.9755
0.0001
0.0015
0.0013
0.0028


105.4
100.9
13.18
98.54
0.0232
0.9707
0.9761
0.0001
0.0016
0.0016
0.0028


106.4
101
11.39
92.28
0.0246
0.9695
0.9760
0.0001
0.0014
0.0016
0.0029


107.4
100.9
9.79
86.54
0.0236
0.9707
0.9764
0.0001
0.0013
0.0014
0.0029


108.4
100.9
12.92
101.64
0.0232
0.9712
0.9762
0.0001
0.0013
0.0013
0.0029


109.4
101.2
11.82
72.14
0.0148
0.9757
0.9755
0.0001
0.0020
0.0026
0.0048


110.4
101.3
6.68
80.24
0.0150
0.9755
0.9753
0.0001
0.0020
0.0025
0.0048


111.4
101.7
7.59
82.75
0.0153
0.9767
0.9757
0.0001
0.0018
0.0021
0.0040


112.4
102.6
6.73
74.00
0.0145
0.9765
0.9725
0.0001
0.0020
0.0024
0.0045


113.4
102.7
11.48
93.50
0.0118
0.9779
0.9736
0.0001
0.0022
0.0029
0.0051


114.4
102.4
8.20
78.03
0.0155
0.9764
0.9745
0.0001
0.0018
0.0020
0.0042


115.4
102.6
9.84
90.31
0.0157
0.9772
0.9747
0.0001
0.0016
0.0017
0.0038


116.4
102.7
9.15
78.96
0.0149
0.9777
0.9740
0.0001
0.0017
0.0019
0.0038


117.4
102.2
10.70
92.24
0.0143
0.9782
0.9728
0.0001
0.0018
0.0019
0.0038


118.4
103.3
8.77
96.93
0.0132
0.9763
0.9744
0.0001
0.0021
0.0025
0.0058


119.4
102
9.19
85.46
0.0126
0.9771
0.9751
0.0001
0.0024
0.0027
0.0051


120.4
102.8
10.32
104.19
0.0134
0.9772
0.9748
0.0001
0.0019
0.0025
0.0048


121.4
102.5
12.94
86.06
0.0132
0.9776
0.9752
0.0001
0.0019
0.0022
0.0050


122.4
102.6
10.78
81.22
0.0132
0.9796
0.9749
0.0001
0.0017
0.0018
0.0037


123.4
103.5
10.27
94.18
0.0155
0.9753
0.9689
0.0001
0.0019
0.0022
0.0051


124.4
104.6
10.24
99.21
0.0181
0.9768
0.9716
0.0001
0.0013
0.0010
0.0027


125.4
103.1
20.25
66.41
0.0171
0.9781
0.9697
0.0001
0.0012
0.0009
0.0026


126.4
103.5
9.73
100.02
0.0173
0.9772
0.9665
0.0003
0.0014
0.0011
0.0027


127.4
103.3
12.31
84.19
0.0166
0.9777
0.9733
0.0001
0.0016
0.0010
0.0031


128.4
102.6
14.89
101.73
0.0176
0.9772
0.9717
0.0001
0.0013
0.0011
0.0027


129.4
103.6
18.07
63.86
0.0164
0.9780
0.9662
0.0003
0.0013
0.0010
0.0030









Example 3
A 2% mix of 1,1,2,3-tetrachloropropene in 98% 2-chloro-3,3,3-trifluoropropene by weight is used early in the run to reduce the activity of the catalyst system, and, thereby, the formation of 1,1,1,2,2-pentafluoropropane. About 2261 grams of new SbCl5 were added into Reactor R11. R11 is a TeflonTM-lined liquid phase reactor (Teflon is a trademark of E.I. duPont de Nemours & Co) equipped with a 2-inch ID (inside diameter) catalyst stripper (a packed column to keep catalyst from escaping from the reactor system). The reactor is 2.75-inch ID×36-inch L (length). The reactor was heated to about 85° C. -87° C. HF feed was started first. After 1.4 lbs (pounds) of HF had been added to fluorinate the catalyst charge, the 2-chloro-3,3,3-trifluoropropene feed was started. The experiment (Run#50) ran continuously for about 22 hours. The HF feed for the run averaged 1.36 lb/hr and the 2-chloro-3,3,3-trifluoropropene feed averaged 0.79 lb/hr. for a 11.2/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 75.2 second residence time. Chlorine was added from time to time in either 2 or 4% by weight of organic amounts to keep the catalyst active in case needed. The reactor temperature range for the experiment was 85-97° C. and the pressure range was 85 psig-115 psig (pounds per square inch gauge). Results are shown in Table 4.







TABLE 4







(Run #50 Conversion and Selectivity on a Molar Basis)

















hours

HF/Org
Residence
molar
molar
molar
molar
molar
molar
molar


el.
Temp
mole
Time,
selectivity
selectivity
Conversion
selectivity
selectivity
selectivity
selectivity


Time
° C.
ratio
seconds
245cb
244bb
1233xf
235da
1232xf
1223xd
others*




















 1
76.8
6.39
47.33
0.0352
0.9125
0.4956
0.0052
0.0117
0.0007
0.0346


 2
81.9
9.07
61.06
0.0421
0.9168
0.6217
0.0034
0.0106
0.0004
0.0267


 3
80.2
10.30
60.38
0.0305
0.9591
0.9152
0.0008
0.0026
0.0003
0.0067


 4
88.7
9.79
60.05
0.0314
0.9035
0.9603
0.0031
0.0403
0.0002
0.0215


 5
91
10.92
60.50
0.0316
0.9283
0.9303
0.0004
0.0165
0.0015
0.0216


 6 *2
92.1
9.65
64.43
0.0524
0.9198
0.8524
0.0004
0.0054
0.0019
0.0202


 7 *3
91.9
10.25
58.67
0.0507
0.9141
0.9142
0.0005
0.0064
0.0031
0.0253


 8 *2
91.1
11.52
66.81
0.0412
0.9201
0.9370
0.0003
0.0139
0.0027
0.0217


 9
89.5
10.15
58.37
0.0283
0.9382
0.9585
0.0017
0.0146
0.0022
0.0150


10
90.3
12.66
61.94
0.0205
0.9355
0.9575
0.0001
0.0142
0.0039
0.0258


11
89.8
10.92
60.50
0.0227
0.9558
0.9622
0.0001
0.0040
0.0022
0.0152


12
89.8
10.58
59.57
0.0252
0.9505
0.9083
0.0002
0.0024
0.0028
0.0189


12.8 *1
89.8
105.05
101.37
0.0218
0.9484
0.9274
0.0002
0.0024
0.0029
0.0243


13.8
89.6
11.19
71.39
0.0240
0.9558
0.9067
0.0004
0.0017
0.0021
0.0161


14.8 *3
89.2
15.90
93.69
0.0225
0.9512
0.9221
0.0004
0.0018
0.0027
0.0214


15.8
888.9
9.65
64.43
0.0187
0.9564
0.9095
0.0005
0.0028
0.0027
0.0190


17.3 *3
90.3
13.73
169.30
0.0174
0.9607
0.9067
0.0004
0.0022
0.0010
0.0182


18.3
90
15.69
87.22
0.0206
0.9633
0.8013
0.0003
0.0022
0.0011
0.0124


19.3 *3
89
12.08
112.24
0.0110
0.9584
0.8700
0.0004
0.0050
0.0036
0.0216


20.3
91.1
10.82
76.64
0.0117
0.9600
0.7583
0.0010
0.0033
0.0068
0.0172


21.3 *3
91
12.42
83.80
0.0044
0.9566
0.9350
0.0009
0.0190
0.0079
0.0111





*1 after Gasbag #12, switched from 2% TCP/1233xf to pure 1233xf


*2 single chlorine addition after Gasbags #5 and 7


*3 double chlorine addition after Gasbags #6, 14, 16, 18, and 20






Example 4
The vapor phase fluorination of the 2-chloro-3,3,3-trifluoropropene (1233xf)+HF→2-chloro-1,1,1,2-tetrafluoropropane(244bb) was carried out. The fluorination catalyst for the experiment was 50 wt % SbCl5 impregnated on 50 wt % Calgon PCB activated carbon.
A total of 2272.6 grams (or about 2800 cc) was charged to two 2-inch vapor-phase pipe reactors in series and installed in a sand bath for controlled heating.
The catalyst was activated by adding a minimum of a 5:1 mole ratio of HF to SbCl5, followed by a Cl2 addition of a minimum of a 3:1 mole ratio of Cl2 to SbCl5. Finally, a large excess of HF was passed through the catalyst bed for 2 hours.
The reaction was run using cylinders of 2-chloro-3,3,3-trifluoropropene crude material as organic feed to produce 2-chloro-1,1,1,2-tetrafluoropropane. The reactor effluent was collected in the distillation column before removal of excess HF. During the experiment, a 93.5% conversion of 2-chloro-3,3,3-trifluoropropene was achieved. The maximum selectivity of 2-chloro-1,1,1,2-tetrafluoropropane achieved was 98.4% on a molar basis. The reaction ran continuously for 76.5 hrs without attempting catalyst regeneration with Cl2. The catalyst began showing signs of deactivation after about 65 hours on-stream time. The reaction conditions and experimental data are shown below in Tables 1A and 1B.















TABLE 1A









1233xf



Contact


On-stream
T
P

feed rate
HF feed rate
HF:1233xf

Time


time (hrs)
(° C.)
(Mpa)
Catalyst
(g/hr)
(g/hr)
mole ratio
Catalyst (ml)
(sec)























 1-23
72
0.33
SbCl5/C
95.3
222.3
15.5
2800
99


23-29
72
0.33
SbCl5/C
145.2
258.6
11.8
2800
84


29-42
72
0.33
SbCl5/C
186.0
290.3
10.3
2800
74


42-53
74
0.33
SbCl5/C
240.4
331.1
9.1
2800
64


53-60
76
0.33
SbCl5/C
322.1
381.0
8.1
2800
54


  60-65.5
77
0.33
SbCl5/C
394.6
480.8
8.3
2800
43


65.5-73.5
80
0.33
SbCl5/C
408.2
485.4
7.9
2800
42


73.5-76.5
79
0.33
SbCl5/C
281.2
426.4
10.5
2800
49


















TABLE 1B







On-




stream


Time
1233xf
Selectivities (molar basis)













(hrs)
conversion
245cb
244bb
1232iso
1223xd
 others





 1-23
89.9
3.9
92.6
NA
0.1
3.2


23-29
93.2
1.6
96.4
NA
0.0
1.8


29-42
93.5
1.2
96.6
NA
0.0
2.0


42-53
92.0
1.1
96.9
NA
0.0
1.9


53-60
83.8
1.0
98.4
0.0
0.0
0.6


  60-65.5
82.8
1.2
98.1
0.0
0.0
0.7


65.5-73.5
81.5
1.3
97.8
0.3
0.0
0.7


73.5-76.5
75.1
1.1
95.5
0.8
0.0
2.6









It should be understood that the foregoing description is only illustrative of the present invention. Various alternatives and modifications can be devised by those skilled in the art without departing from the invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances that fall within the scope of the appended claims

## Claims

1. A continuous process for hydrofluorinating 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane, comprising: contacting the 2-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of a catalyst having about 25 to about 99.9 mole percent antimony pentachloride and about 0.1 to about 75 mole percent of a metal of a Lewis acid under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane, wherein a conversion of greater than about 45 mole percent 2-chloro-3,3,3-trifluoropropene and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than 30 hours from initiation of the contacting step.

2. The process of claim 1, wherein the metal of a Lewis acid is selected from the group consisting of SbCl3, TiCl4, SnCl4, TaCl5, NbCl5, NbCl3, ZrCl4, and HfCl4.

3. The process of claim 1, wherein the Lewis acid is SbCl3.

4. The process of claim 1, wherein the catalyst is fluorinated.

5. The process of claim 1, wherein the catalyst has about 50 to about 98 mole percent antimony pentachloride and about 2 to about 50 mole percent Lewis acid.

6. The process of claim 1, wherein the hydrofluorination is carried out at a temperature of about 30° C. to about 200° C.

7. The process of claim 1, wherein the hydrofluorination is carried with a residence time of from about 30 seconds to about 240 seconds.

8. The process of claim 1, wherein a conversion of greater than about 45 mole percent 2-chloro-3,3,3-trifluoropropene and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than about 15 hours from initiation of the contacting step.

9. The process of claim 1, wherein a conversion of greater than about 45 mole percent 2-chloro-3,3,3-trifluoropropene and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than 12.4 hours from initiation of the contacting step.

10. The process of claim 1, wherein a conversion of greater than about 45 mole percent 2-chloro-3,3,3-trifluoropropene and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than 3.1 hours from initiation of the contacting step.

11. A continuous process for making 2-chloro-1,1,1,2-tetrafluoropropane, comprising: hydrofluorinating about 75 to about 99.9 mole percent 2-chloro-3,3,3-trifluoropropene and about 0.1 to about 25 mole percent of one or more other hydrocarbons having at least one chlorine atom in the presence of a catalyst of antimony pentachloride under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane, wherein a conversion of greater than about 50 mole percent 2-chloro-1,1,1,2-tetrafluoropropane and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than 30 hours from initiation of the contacting step.

12. The process of claim 11, wherein the one or more hydrocarbons are selected from the group consisting of 1,1,2,3-tetrachloropropene; 2,3-dichloro-3,3-difluoropropene; 2,3,3-trichloro-3-fluoropropene; and 1,1,1,2,3-pentachloropropane.

13. The process of claim 12, wherein the one or more hydrocarbons is 1,1,2,3-tetrachloropropene.

14. The process of claim 11, wherein the hydrofluorination is carried out at a temperature of about 30° C. to about 200° C.

15. The process of claim 11, wherein the hydrofluorination is carried with a residence time of from about 30 seconds to about 240 seconds.

16. The process of claim 11, wherein the catalyst is fluorinated.

17. The process of claim 11, wherein a conversion of greater than about 50 mole percent 2-chloro-1,1,1,2-tetrafluoropropane and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than about 16 hours from initiation of the contacting step.

18. The process of claim 11, wherein a conversion of greater than about 50 mole percent 2-chloro-1,1,1,2-tetrafluoropropane and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than about 5 hours from initiation of the contacting step.

19. The process of claim 11, wherein a conversion of greater than about 50 mole percent 2-chloro-1,1,1,2-tetrafluoropropane and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than one hour from initiation of the contacting step.

20. A continuous process for hydrofluorinating 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane, comprising: contacting the 2-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of a vapor phase catalyst under conditions sufficient to form the 2-chloro-1,1,1,2-tetrafluoropropane, wherein a conversion of greater than about 80 mole percent 2- chloro-3,3,3-trifluoropropene and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than 30 hours from initiation of the contacting step.

21. The process of claim 20, wherein the catalyst is fluorinated.

22. The process of claim 20, wherein the catalyst has about 25 to about 99.9 mole percent antimony pentachloride and about 0.1 to about 75 mole percent Lewis acid.

23. The process of claim 20, wherein the 2-chloro-3,3,3-trifluoropropene is provided in the form of a feed stream having about 75 to about 99.9 mole percent 2-chloro-3,3,3-trifluoropropene and about 0.1 to about 25 mole percent of one or more other hydrocarbons having at least one chlorine atom.

24. The process of claim 20, wherein the hydrofluorination is carried out at a temperature of about 30° C. to about 200° C.

25. The process of claim 20, wherein the hydrofluorination is carried at a residence time of from about 10 seconds to about 240 seconds.

26. The process in claim 20, wherein the catalyst is supported.

27. The process in claim 23, wherein the catalyst support is selected from the group consisting of carbon, alumina, fluorinated alumina, aluminum fluoride, alkaline earth metal oxides, fluorinated alkaline earth metals, zinc oxide, zinc fluoride, tin oxide, and tin fluoride.

28. The process of claim 20, wherein the catalyst is activated prior to use.

29. The process of claim 20, wherein a conversion of greater than about 80 mole percent 2-chloro-3,3,3-trifluoropropene and a selectivity of less than about 15 mole percent for each by-product other than 2-chloro-1,1,1,2-tetrafluoropropane is achieved in less than 23 hours from initiation of the contacting step.